ES2290444T3 - COMPOSITIONS OF FORMATION OF WATER SUPPORT FILM THAT INCLUDES COPOLYMERS CONTAINING MONOBBERS OF ISOBUTILENE TYPE. - Google Patents

Abstract

A curable aqueous film forming composition comprising: a) a polymeric binder containing two or more reactive functional groups; b) a curing agent having at least two functional groups that are reactive with the reactive functional groups of (a); and c) a copolymer flow control agent comprising at least 30 mol% of radicals having the following alternating structure - [DM-AM] - in which DM represents a radical of a donor monomer and AM represents a radical of an acceptor monomer; having at least 15 mol% of the copolymer comprising donor monomer the following structure (I): (See formula) in which R 1 is a linear or branched C 1 to C 4 alkyl, R 2 is selected from the group consisting in methyl, linear, cyclic or branched C1 to C20 alkyl, alkenyl, aryl, alkaryl or aralkyl.

Description

Film formation compositions of aqueous support comprising copolymers containing monomers of isobutylene type.

Background of the invention 1. Field of the invention

The present invention relates in a manner general to the use of copolymers of ethylenically monomers unsaturated in support film forming compositions aqueous. More specifically, the present invention relates to aqueous support film forming compositions that comprise copolymers containing monomers of type isobutylene

2. Description of the prior art

It is often observed that the monomers that do not homopolymerize easily can experience reactions of rapid copolymerization with each other. The most typical situation occurs when a strong electron donor monomer is mixed with a strong electron acceptor monomer from which results in a regular alternating copolymer after radical initiation free. Maleic anhydride is a widespread example of strong electron acceptor monomer. Styrene and ethers vinyl are typical examples of donor monomers of electrons Systems are known, such as maleic anhydride - styrene, which form charge transfer complexes, which they have to place the monomer in an alternating sequence before the initiation. The free radical initiator application "tie" the monomers ordered together to form a copolymer alternating (Cowie, Alternating Copolymers, Plenum, New York (1985).

In the US patents No. 2,378,629 for Hanford and 4,151,336 for Sackmann et al. it is described that even when copolymerizes an electron donor monomer moderately, such as for example diisobutylene, with an electron acceptor monomer strong, like maleic anhydride, the result is a copolymer alternating

When a monomer is copolymerized moderately electron donor, such as isobutylene, with a monomer moderately electron acceptor, such as acrylic ester, the result is a scarce incorporation of the donor monomer of electrons For example, free radical copolymerization of Isobutylene (IB) and acrylic monomers have resulted in copolymers containing at most 20-30% of IB and which have low molecular weights, due to the transfer of IB degradation chain. In the US patents No. 2,411,599 for Sparks et al. and 2,531,196 for Brubaker et al. They describe examples of said IB copolymerizations.

It is desirable to have the ability to obtain copolymers of acrylic monomers and monomers of type IB within The technique. For example, many patents express the potential that involves the use of polymers with IB content for compositions of coating. As an illustration of this, in US Pat. nº 6,114,489 for Vicari et al. a composition of coating that includes an acrylic resin binder functional, a co-reagent capable of reacting with the functionality of the acrylic binder; a degasser; a leveling agent and polyester flow hyperbranched IB is suggested as a potential co-monomer for use in the binder Acrylic as part of a long list of monomers. In the patent USA No. 5,552,487 to Clark et al., Compositions are described powder coating that include a copolymer having a reactive functionality and a suitable crosslinking agent capable of react with the reactive functionality of the copolymer. He copolymer is obtained by copolymerization of functional monomers with other monomers, isobutylene being one among the many listed as potential co-monomers. Though here only two of them, of the many patents that express the possibility of using isobutylene co-monomers, no sample or describes a practical example of said copolymer.

The fact of finding some examples of copolymers containing isobutylene monomer content are due to the generally non-reactive nature of isobutylene with monomers Acrylic or methacrylic. The reactivity relationships for monomers can be calculated using Alfrey values - Price Q-e (Robert Z. Greenley, Polymer Handbook, fourth edition, Brandrup, Immergut and Gulke, editors, Wiley & Sons, New York, NY, pp. 309-319 (1999)). The calculation is It can be carried out by applying formulas I and II:

Ir_ {1} = (Q_ {1} / Q_ {2}) exp {-e_ {1} (e_ {1} -e_ {2})}

IIr_2 = (Q_ {2} / Q_ {1}) exp - {- e_ {2} (e_ {2} -e_ {1})}

where r_ {1} and r_ {2} are the reactivity ratios of monomers 1 and 2 corresponding, and Q_ {1} and Q_ {2} and e_ {1} and e_ {2} are the reactivity and polarity values for the corresponding monomers respectively (Odian, Principals of Polymerization, 3rd ed. Wiley-Inter-Science, New York, NY, chapter 6, pp. 452-467 and 489-491 (1991)). Table 1 shows the calculated reactivity ratios of selected monomers with isobutylene:

TABLE 1

one

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As specialists in the polymer chemistry technique, when r_ {1} is close to zero and R2 has a value of 10 or higher, monomer 2 is reactive towards both monomers and monomer 1 is not reactive towards None of the monomers. That is, it is extremely difficult prepare copolymers that have significant amounts of both monomers It shouldn't surprise you that some can be found examples of coating compositions that include copolymers with monomer content of isobutylene type, since the monomers They do not usually copolymerize.

Some examples of copolymers of acrylic ester or acrylonitrile obtained by copolymerization with monomers such as propylene, isobutylene and styrene, in the presence of Lewis acids, such as alkylaluminum halides, for give alternating copolymers 1: 1. The alternating copolymers are obtained when the Lewis acid concentration ratio to Acrylic esters was 0.9 and the concentration of IB was greater than the concentration of acrylic esters (Hirooka et al., J. Polym Sci. Polym. Chem., 11, 1281 (1973)). Metal halides they vary the reactivity of the monomers when complexing with them. The metal-monomer halide complex donor of electrons - electron acceptor monomer leads to copolymers alternating (Mashita et al., Polymer, vol. 36, No. 15, pp. 2973-2982 (1995)).

IB copolymers have also been obtained and methyl acrylate (MA) using ethyl aluminum sesquichloride and 2-methyl pentanoyl peroxide as a system of initiation. The resulting copolymer had a structure alternating, with both low isotacticity (Kuntz et al., J. Polym. Sci. Polym. Chem. 16, 1747 (1978)) as high in the presence of EtAlCl2 (10% molar relative to MA). (Florjanczyk et al., Makromol Chem. 183, 1081 (1982)).

Another method to obtain IB copolymers with Acrylic esters have involved alkyl boron halide, which as has observed it was much more active than alkyl aluminum halides in the formation of alternating copolymers. The copolymer resulting was an elastomer with high tensile strength and a high temperature of thermal decomposition with a good oil resistance, especially at high temperatures (Mashita et al. Polymer, 36, 2983 (1995)).

In the US patent No. 5,807,937 for Matyjaszewski et al., Describes a method for obtaining alternating copolymers of isobutylene and methyl acrylate using a radical polymerization process by atomic transfer (ATRP). The method requires the use of a suitable ATRP initiator, such as bromide 1-phenylethyl, and transition metal salts suitable, as CuBr, as a ligand, as 2,2'-bipyridyl, to carry out the steps of initiation of redox complex and propagation of the process of polymerization.

Copolymers containing amounts relatively high (? 30% moles) of IB and acrylic esters are have obtained only by free radical polymerization when Lewis acids and initiation systems have been used ATRP. The polymer resulting from these processes requires a expensive cleaning and it takes time to remove waste from the transition metal salt and / or Lewis acid in order to obtain a commercially useful polymer.

The coating compositions, liquid and powder coatings for example, are used in a wide range of applications, including, for example, cars, appliances and industrial markets. The coatings are frequently used to provide a decorative quality and / or corrosion protection substrates on which they are applied. In correspondence, typically it is necessary that the applied coatings have at least one continuous flawless surface. The automotive industry demands particularly strict requirements as regards the uniformity of the coatings used, as in the case of compositions for transparent layers for car.

The coating compositions contain typically a flow control agent (also called flow modifier) to improve the appearance of the coating cured. Flow control agents have properties superficially active and believed to improve the appearance of a cured coating by altering the flow and leveling of the coating applied during its curing cycle. The agents of flow control containing functional groups, such as acid groups carboxylic and / or hydroxyl groups, are known and, in addition to favor the appearance, can improve the adhesion of the coating to the substrate on which they are applied, and / or improve adhesion or compatibility of a coating that is applied later.

Typically, it is necessary that the compositions coating provide optimal properties, such as the appearance and / or corrosion resistance, with a thickness of the minimum film For example, within the automotive industry, typically it is necessary for transparent top layers have cured film thicknesses not exceeding 50 micrometers (2 mils). The advantages associated with applied coatings with a lower film thickness include for example a smaller cost of materials and a gain in weight of the coated article, what is particularly desirable within the industry aeronautics. However, when the body of the film of an applied coating composition, the appearance of the resulting cured coating typically decreases, by example, as evidenced by more measured brightness values low.

In addition to the application of coatings with lower film bodies, research and development in the last few years have been directed towards reducing the impact environmental of the coating compositions, in in particular, the associated air emissions of organic substances volatile during use. Therefore, interest in coatings that have a lower content of organic substances volatile (VOC), for example, aqueous support coatings and coatings with high solids content, has been increased. In the absence of solvents that can favor the flow and applied coating leveling, a control agent of the flow can constitute a critical component in a composition of aqueous support film formation.

The copolymer compositions containing Lewis acids and / or transition metals intermingled with the copolymer can have a number of drawbacks when used commercially, as coatings for example. In First, some Lewis acids and transition metals are toxic and may have negative effects on the environment if they are filtered from the copolymer and passed into the environment. In second place, in coating applications, Lewis acids and transition metals can lead to poor stability when exposed to UV light or simply cause discoloration of the coating. In other applications, Lewis acids and transition metals can react with other ingredients of the formulation with the result of unwanted properties, such as a shortening of storage life for A given formulation.

It would therefore be desirable to provide copolymers that contain monomers of isobutylene type for use as additives of flow control. However, said copolymers may not Obtained through the use of Lewis acids and / or metals of transition as catalysts and preferably are substantially free of Lewis acids and / or metals of transition, in order to overcome the inconveniences associated with the use of Lewis acids and / or transition metals in compositions of coating.

Compendium of the invention

The present invention relates to compositions film-forming, aqueous (aqueous support), curable that include:

a) a polymeric binder containing two or more reactive functional groups;

b) a crosslinking agent that has at least two functional groups that are reactive with the functional groups reagents of (a); Y

c) a copolymer flow control agent comprising at least 30 mol% of radicals having the next alternating structure

- [DM-AM] -

DM representing a radical of a donor monomer and AM, a radical of an acceptor monomer. At least 15 mol% of the compolymer comprises at least one monomer donor that has the following structure (I):

2

wherein R 1 is an alkyl of C 1 - to C 4 linear or branched, R 2 is selected from group consisting of methyl, linear C 1 to C 20 alkyl, cyclic or branched, alkenyl, aryl, alkaryl or aralkyl. In a specific embodiment, at least 15 mol% of the Copolymer comprises an acrylic monomer as an acceptor monomer. He copolymer may contain at least one salt group or a group of salt formation to favor water dispersibility. The copolymer composition is preferably substantially free of Lewis acids and metals from transition.

A composition of multi-component composite coating comprising a base layer deposited from a formation composition of pigmented film and a transparent top layer applied on the base layer The top layer is deposited from the film forming composition that has been described.

Detailed description of the invention

Except for practical examples, or not otherwise stated, all numbers or expressions which refer to quantities of ingredients, conditions of reaction, etc. used in the specification and in the claims have to be understood as modified in all cases for the term "approximately". Several are described numerical intervals in the present patent application. Given the these intervals are continuous, include all values between the minimum and maximum values. Unless I know expressly indicate different intervals Numerals specified in this application are approaches.

The curable film formation composition of the present invention may consist of any composition of aqueous support useful in coating applications, in particular, automobile applications, as they know the people specialized in the technique. Among the resins of particularly useful polymeric film formation suitable Acrylic polymers are included for the polymer binder (a), polyesters, including alkyds and polyurethanes. Generally, these polymers can consist of any polymer of these types obtained through any of the known methods among the people specialized in the technique, being the water dispersible or emulsifiable polymers, preferably of limited water solubility. The functional groups of polymeric binder (a) may be selected from the group that consists of hydroxyl, carbamate, blocked isocyanate, amine primary, secondary amine, amide, urea, urethane, vinyl and mixtures from them.

Among the suitable acrylic polymers are include copolymers of one or more alkyl acid esters acrylic or methacrylic acid, optionally, in combination with one or more polymerizable ethylenically unsaturated monomers. Between suitable acrylic or methacrylic acid alkyl esters are include aliphatic alkyl esters containing 1 to 30, preferably from 4 to 18 carbon atoms in the alkyl group. Non-limiting examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethyl hexyl acrylate. Other suitable examples of ethylenically unsaturated monomers Copolymerizable include vinyl aromatic compounds, such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides and vinylidene such as vinyl chloride and fluoro vinylidene; and vinyl esters such as vinyl acetate.

The acrylic copolymer can include groups hydroxyl functional, which are frequently incorporated into the monomer including one or more monomers with hydroxyl function in the reagents used to produce the copolymer. Between the hydroxyl monomers include acrylates and methacrylates of hydroxyalkyl, which typically have 2 to 4 atoms of carbon in the hydroxyalkyl group, such as, for example, acrylate of hydroxyethyl, hydroxypropyl acrylate, acrylate 4-hydroxybutyl, hydroxy function adducts of Caprolactone and hydroxyalkyl acrylates and methacrylates corresponding, as well as monomers with function beta-hydroxy ester described below. The acrylic polymer can also be prepared with N- (alkoxymethyl) acrylamides and N- (alkoxymethyl) methacrylamides.

The monomers with function beta-hydroxy ester can be prepared from ethylenically unsaturated and acidic epoxy monomers carboxylics having from about 13 to about 20 carbon atoms and monomers with ethylenically acid function unsaturated and epoxy compounds containing at least 5 atoms of carbon that are not polymerizable with the acid-functional monomer ethylenically unsaturated.

Among the monomers with epoxy function ethylenically unsaturated useful for preparing monomers with beta-hydroxy ester function are included without limitation only to them glycidyl acrylate, glycidyl methacrylate, ether glycidyl allyl, glycidyl metalyl ether; 1: 1 (molar) adducts of ethylenically unsaturated monoisocyanates with monoepoxides with hydroxy function such as glycidol and acid glycidyl esters polymerizable polycarboxylic acids, such as maleic acid. They are Preferable glycidyl acrylate and glycidyl methacrylate. Between Examples of carboxylic acids are included, not limited only to them, saturated monocarboxylic acids such as isostearic acid and aromatic unsaturated carboxylic acids.

Among the monomers with acid function ethylenically unsaturated useful used to prepare monomers with beta-hydroxy ester function are included monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; dicarboxylic acids such as itaconic acid, acid maleic and fumaric acid; and monoesters of dicarboxylic acids as monobutyl maleate and monobutyl itaconate. Typically, the monomer with ethylenic acid function is reacted unsaturated and the epoxy compound in an equivalent 1: 1 ratio. He epoxy compound does not contain an ethylenic unsaturation that can participate in free radical initiated polymerization with the monomer with unsaturated acid function. Among the epoxy compounds useful include 1,2-pentene oxide, oxide styrene and glycidyl esters or ethers, which contain preferably from 8 to 30 carbon atoms, such as ether butyl glycidyl, octyl glycidyl ether, phenyl glycidyl ether or para- (tert-butyl) phenyl glycidyl ether. The Preferred glycidyl esters include those presenting the structure:

3

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in which R is a radical hydrocarbon containing from about 4 to about 26 carbon atoms Preferably, R is a hydrocarbon group branched that has about 8 to about 10 carbon atoms, such as neopentanoate, neoheptanoate or neodecanoate. Among the glycidyl esters of suitable carboxylic acids are include VERSATIC ACID 911 and CARDURA E, which are distributed in the trade by Shell Chemical Co.

Groups may be included in the acrylic polymer functional carbamate copolymerizing the acrylic monomers with a vinyl monomer with carbamate function, such as ester alkyl with methacrylic acid carbamate function, or by making reacting an acrylic polymer with hydroxyl function with a material with low molecular weight carbamate function, so that can be derived from an alcohol or glycol ether through a transcarbamoylation reaction. In this reaction, it is done react a material with low molecular weight carbamate function derived from an alcohol or glycol ether with the hydroxyl groups of the acrylic polyol, to produce an acrylic polymer with carbamate function and the original alcohol or glycol ether. He material with low molecular weight carbamate function derived from a alcohol or glycol ether can be prepared by reacting to alcohol or glycol ether with urea in the presence of a catalyst. Suitable alcohols include aromatic alcohols, low molecular weight cycloaliphatic and aliphatic, such as methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexane and 3-methylbutanol. Suitable glycol ethers include methyl ether of ethylene glycol and propylene glycol methyl ether. They are used over all methyl ether of propylene glycol and methanol. Other monomers with Suitable carbamate function are those described in the patent USA No. 5,098,947, which is incorporated herein as reference. Other useful carbamate monomers are described in US Pat. No. 5,098,947.

Amide functionality can be entered in the acrylic polymer using suitable functional monomers in the polymer preparation, or converting other functional groups to Amido groups using known techniques among people specialized in the technique. Similarly, they can be incorporated other functional groups as desired using monomers functional functions, if available or from reactions of Conversion as required.

Acrylic polymers can be prepared at through aqueous emulsion polymerization techniques and be used directly in the preparation of compositions of aqueous coating, or can be prepared through techniques of polymerization in organic solution with groups capable of forming salt as, for example, acid or amine groups. After neutralization of these groups with a base or an acid, the polymers in aqueous medium. Generally, you can use any production method of said polymers that is known among the people skilled in the art using the amounts of the monomers recognized in the art.

In addition to acrylic polymers, the resin of polymer film formation suitable for the binder Polymeric (a) in the coating composition may consist of an alkyd resin or a polyester. Such polymers can be prepare in a suitable manner by condensation of alcohols polyhydroxy and polycarboxylic acids. Between the alcohols Suitable polyhydroxyls are included without being limited only to them ethylene glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane and pentaerythritol. Between the Suitable polycarboxylic acids are included, not limited only to them, succinic acid, adipic acid, azelaic acid, acid sebacic acid, maleic acid, fumaric acid, phthalic acid, acid tetrahydrophthalic, hexahydrophthalic acid and trimellitic acid. In addition to the polycarboxylic acids that have been mentioned, they can use functional equivalents of acids, as per example anhydrides, where they exist, or lower alkyl esters of acids such as methyl esters. When desired produce air drying alkyd resins, can be used Suitable oily drying fatty acids, including for example those derived from linseed oil, soybean oil, such oil, dehydrated castor oil or tung oil.

Groups with function can be incorporated carbamate in the polyester first forming a carbamate of hydroxyalkyl that can be reacted with the polyacids and Polyalcohols used in the formation of polyester. Condenses hydroxyalkyl carbamate with acid functionality in the polyester, to produce terminal carbamate functionality. Too groups with carbamate function can be incorporated in the polyester by reacting the terminal hydroxyl groups in the polyester with a material with low molecular weight carbamate function a through a transcarbamoylation process similar to the one that has been described above in connection with the incorporation of groups carbamate in acrylic polymers, or by acid reaction isocyanic with a polyester with hydroxyl function.

They can also be incorporated in polyester or alkyd resin other functional groups such as isocyanate blocked, primary amine, secondary amine, amide, urea and urethane, as desired, using suitable functional reagents, if are available, or by conversion reactions as necessary, to produce the desired functional groups. These techniques are known among people specialized in technique.

Polyurethanes can also be used as polymeric binder (a) in the formation composition of film of the present invention. Among the polyurethanes that they can use polymer polyols that are included they usually prepare by reacting the polyester polyols or acrylic polyols, such as those mentioned above, with a polyisocyanate, so that the OH / NCO equivalent ratio is greater than 1: 1 so that they are free hydroxyl groups present in the product. Polyisocyanate organic used to prepare polyurethane polyol it may consist of an aliphatic or aromatic polyisocyanate or a mix of the two. Diisocyanates are preferable, although they can use higher polyisocyanates instead of diisocyanates or in combination with them. Among the examples of Suitable aromatic diisocyanates include diisocyanate 4,4'-diphenylmethane and toluene diisocyanate. Between Examples of suitable aliphatic diisocyanates are included. straight chain aliphatic diisocyanates, such as diisocyanate 1,6-hexamethylene. They can also be used cycloaliphatic diisocyanates. Examples include isophorone diisocyanate and 4,4'-methylene-bis- (diisocyanate cyclohexyl). Among the examples of higher polyisocyanates Suitable include 1,2,4-benzene triisocyanate and polymethylene polyphenyl isocyanate. As regards the polyesters, polyurethanes can be prepared with the groups unreacted carboxylic acids which, after neutralization with base such as amines, allows dispersion in aqueous medium.

Groups with function can be incorporated carbamate terminals and / or earrings in the polyurethane making reacting a polyisocyanate with a polymeric polyalcohol that Contains the terminal / pending carbamate groups. Alternatively, groups with carbamate function can be incorporated in the polyurethane by reacting a polyisocyanate with a polyalcohol and a hydroxyalkyl carbamate or isocyanic acid as separate reagents Groups can also be incorporated with carbamate function in the polyurethane by reacting a polyurethane with hydroxyl function with a material with function low molecular weight carbamate through a process of transcarbamoylation similar to that described above in connection with the incorporation of carbamate groups in the acrylic polymer. Additionally, a polyurethane with function can be reacted isocyanate with a hydroxyalkyl carbamate to produce a polyurethane with carbamate function.

Other functional groups can be incorporated as blocked isocyanate, primary amine, secondary amine, amide and urea in the polyurethane, as desired, using reagents functional features, if available or by reactions of conversion, as necessary, to produce the groups desired functional. These techniques are known among the people specialized in the technique.

The support coating composition Aqueous of the present invention may be cationic, anionic or not. ionic, although typically it is anionic. In the US patent No. 4,403,003, support coating compositions are described suitable aqueous, being able to use the resinous compositions Polymers used in the preparation of these compositions as a polymeric binder (a) in the practice of the invention. Also, aqueous support polyurethanes can be used as those prepared according to US Pat. No. 4,147,679 as polymeric binder (a) in the coating composition of the present invention It is also possible to prepare a dispersion aqueous of a mixture of acrylic and polyester and / or materials polyurethane in the form of microparticles through a technique of high voltage using a homogenizer. This technique is preferably used to prepare the composition of coating of the present invention and is described in the patent USA No. 5,071,904.

In this technique, the polymeric binder (a) is a latex comprising polymeric microparticles prepared by forming a mixture in aqueous medium. The mixture contains an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers with more than 30 percent by weight of a substantially hydrophobic polymer. The weight percentage is based on the total weight of the ethylenically unsaturated monomer (s) and the hydrophobic polymer. It is especially preferable that the hydrophobic polymer be essentially free of vinyl or acrylic units that are repeated in the polymer backbone and have a number average molecular weight greater than about 300, as determined by permeation chromatography of gel using a polystyrene pattern. The hydrophobic polymer is preferably a polyester or polyurethane. The monomer (s) and the hydrophobic polymer are fragmented into microparticles through high voltage techniques using a homogenizer followed by polymerization of ethylenically unsaturated monomer (s) to form polymeric microparticles that are dispersed stably in the aqueous medium. These microparticles can be internally crosslinked to form
microgels

The polymeric binder (a) is present generally in the film forming composition in amounts between approximately 55 and 99 percent in weight, typically between about 55 and 90 percent by weight, being more frequent between approximately 55 and approximately 85 weight percent based on total solids weight of resin film forming composition.

As mentioned above, the aqueous support film forming composition of the The present invention further includes (b) a crosslinking agent that It has at least two functional groups that are reactive with functional groups of the polymeric binder a (a). Between the suitable crosslinking agents include aminoplasts, polyisocyanates, polyacids, anhydrides and mixtures thereof. The Suitable aminoplast resins are based on the products of addition of formaldehyde with a substance that carries an amino group or amide. The condensation products obtained from the reaction of alcohols and formaldehyde with melamine, urea or benzoguanamine are the most common and preferable here. While the aldehyde used is more often formaldehyde, others can be obtained similar condensation products from other aldehydes, like acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal and the like.

You can also use the products of condensation of other amines and amides, such as aldehyde condensates of triazines, diazines, triazoles, guanadines, guanamines and alkyl and aryl substituted derivatives of said compounds, including alkyl substituted ureas and aryl and melamines substituted with alkyl and aryl. Between the non-limiting examples of said compounds are included N, N'-dimethyl urea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, glucoluril, ameline, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine and carbamoyl triacines of the formula C 3 N 3 (NHCOXR) 3 in which X is nitrogen, oxygen or carbon, and R is a lower alkyl group that it has one to twelve carbon atoms or mixtures of alkyl groups lower, such as methyl, ethyl, propyl, butyl, n-octyl and 2-ethylhexyl. Sayings Compounds and their preparation are described in detail in the patent USA No. 5,084,541, which is incorporated herein as reference.

Aminoplast resins contain preferably methylol or similar alkylol groups and, in most  of the cases, at least a portion of these alkylol groups are etherified by reaction with an alcohol. Can be used any monohydric alcohol for this purpose, including methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, as well as a benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, glycol monoethers and halogen substituted alcohols and other substituted alcohols such as 3-chloropropanol and butoxyethanol. The resins of Preferable aminoplast are partially alkylated with methanol or butanol

Polyisocyanate crosslinking agents are they can prepare from various materials with content in isocyanate Most often, polyisocyanate is a blocked polyisocyanate. Among the examples of polyisocyanates Suitable trimers prepared from the following are included diisocyanates; toluene diisocyanate, 4,4'-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, an isomeric mixture of diisocanate from 2,2,4- and 2,4,4-trimethyl hexamethylene diisocyanate 1,6-hexamethylene tetramethyl diisocyanate xylylene, and 4,4'-diphenylmethylene diisocyanate. On the other hand, the prepolymers of blocked polyisocyanate of various polyols such as, for example, polyester polyols. Among the examples of blocking agents suitable materials are included that would unlock high temperatures, such as aliphatic alcohols lower ones including methanol, oximes, such as methyl ethyl ketoxime, lactams like caprolactam and pyrazoles like 3,5-dimethyl pyrazole.

Among the examples of polycarboxylic acids which are suitable for use as a crosslinking agent in the aqueous curable film forming composition of the present The invention includes those described in US Pat. nº 4,681,811, in column 6, line 45 to column 9, line 54. Enter suitable polyanhydrides include those described in the US patent No. 4,798,746, in column 10, lines 16-50, and in US Pat. No. 4,732,790, in the column 3 lines 41-57.

Generally, the crosslinking agent (b) is present in an amount between approximately 1 and approximately 45 percent by weight based on the total weight of the resin solids of the film forming composition, typically from about 10 to about 45 percent in weight and, more frequently from about 15 to about 45 percent by weight.

In an embodiment of the invention, the film forming composition of the invention comprises the minus a thermostable aqueous dispersion containing polymeric microparticles as component (a) that has a functionality adapted to react with an agent reticulation. In particular, components (a) and (b) are substantially hydrophobic and are prepared as an aqueous dispersion comprising polymeric microparticles, prepared by mixing of components (a) and (b) in combination under high conditions shear before or simultaneously with the incorporation of the agent of flow control (c). The film formation composition is capable of forming a generally continuous film at temperature ambient.

As used here, the term "dispersion" means that the microparticles are capable of distributed throughout the water as finely divided particles, such as in a latex. Consult Condensed Chemical Hawley's Dictionary (12th edi, 1993) on page 435, which is incorporated herein by reference. Uniformity of the dispersion can be increased by adding agents of wetting, dispersion or emulsification (surfactants), which will be explained later.

The polymeric microparticles are prepared mixing at high shear conditions (a) at least one substantially hydrophobic polymeric binder having groups functional reagents, such as groups with acid function; Y (b) at least one hydrophobic crosslinking agent containing groups functional reactants with the functional groups of the binder polymeric. As used here, the expression "with acid function "means that the polymeric binder (a) it contains groups that can give up to a proton to a base in a chemical reaction; a substance that is able to react with a base to form a salt; or a compound that produces ions hydronium, H 3 O +, in aqueous solution. Consult the Hawley at  page 15 and K. Whitten et al., General Chemistry, (1981) in the page 192.

The term "substantially hydrophobic" such as used herein means that the material so described is essentially not compatible with water, or has no affinity for water, and / or is not able to dissolve in water using the means of Conventional mixing That is, after mixing the sample of the material with an organic component and water, a majority of material is in the organic phase and a phase is observed separate watery. Consult the Condensed Chemical Dictionary of Hawley (12th ed. 1993) on page 618.

Typically, the acid number of the binder hydrophobic polymer (a) is below 50, often the acidity index is below 25, more frequently it oscillates between 10 and 20. The amount of acid functionality in a resin is It can measure according to the acid number. As used here and in the claims, "acid number" refers to the number of milligrams of KOH per gram (mg KOH / g) of the solid required to neutralize the acidic functionality of the resin. So that the hydrophobic polymer is substantially hydrophobic, the polymer hydrophobic should not contain enough acidic or ionic functionality as to allow them to form stable dispersions in the water using conventional dispersion techniques. It must also  understood that in the case that the acid value of the polymer hydrophobic is approximately 0, an agent can be used suitable surfactant to stably disperse the polymer in aqueous media applying high voltage techniques. The agents anionic, cationic and non-ionic surfactants are suitable for its use in the aqueous dispersions of the present invention, with anionic surfactants being preferred. Between the non-limiting examples of suitable anionic surfactants acid dimethylethanolamine salt included dodecylbenzenesulfonic acid, dioctyl sulphosuccinate sodium, salts of ethoxylated nonylphenol sulfate and sodium dodecylbenzene sulphonate. Polymeric surfactants can also be used. The surfactants that have been described are present typically in the dispersion in an amount less than 2 per weight percent, preferably less than 1 weight percent, in function of the total weight of the resin solids present in the dispersion.

Hydrophobic polymers that have indices of Low acidity can be considered as dispersible in water if they contain other hydrophilic components such as groups hydroxyl or poly (ethylene oxide) groups, in an amount enough to effect the dispersibility of the polymer in aqueous media. However, it should be understood that for purposes of the present invention, said polymers are not considered as substantially hydrophobic if they are dispersible in water, regardless of its acid number.

The substantially polymeric binder hydrophobic (a) may consist of a prepared acrylic polymer using the monomers that have been described.

In a particular embodiment, it is first form the polymeric binder (a) and then combined with the hydrophobic crosslinking agent (b) explained in more detail below, and added to the aqueous medium to form a pre-emulsion mixture. Generally add a neutralizing agent to the agent mixture crosslinking / polymer before combining it with the aqueous medium to facilitate dispersion. Alternatively, the binder is formed. Polymeric (a) by free radical initiated polymerization in presence of hydrophobic crosslinking agent (b). Must be understood that when preparing the polymeric binder (a) in the presence of the hydrophobic crosslinking agent (b), the reaction product final is considered as of equal composition, characteristics and physical properties that if previously formed under the conditions  of polymerization of conventional free radicals.

The appropriate methods for homo- and copolymerization of ethylenically unsaturated monomers and / or others addition polymerizable monomers and polymers pre-trained are well known among people specialized in the technique of polymers and is not considered further explanation necessary in view of this description. For example, polymerization can be carried out of ethylenically unsaturated monomers in a solution of organic or aqueous mass solvent such as xylineo, methyl isobutyl ketone and n-butyl acetate, in emulsion, or in a aqueous dispersion Kirk-Othmer Encyclopedia of Chemical Technology, vol. 1 (1963) on page 305. The polymerization can be carried out by means of a system suitable initiator, which typically includes the initiators of free radicals, such as benzoyl peroxide or azobisisobutyronitrile. Molecular weight can be controlled selecting the solvent or polymerization medium, the concentration of initiator or monomer, temperature and use of chain transfer agents. If major is required information, said polymerization methods are described in Kirk-Othmer, vol. 1 on pages 203-205, 259-297 and 305-307.

The number average molecular weight of the preformed hydrophobic polymer binder it can range between about 500 and about 100,000, preferably between about 1,000 and about 10,000 Unless stated otherwise, weights molecular, as used herein and in the claims, they are expressed as molecular weights in number average as determined by gel permeation chromatography using polystyrene as a pattern.

The glass transition temperature (Tg) of hydrophobic polymeric binder (a) is typically less than 100 ° C, often below 50 ° C, more frequently below 35 ° C, even more frequently below 30 ° C, being mostly frequent below 25 ° C. The Tg of the polymeric binder hydrophobic (a) is typically at least -50 ° C, often at minus -25ºC, more frequently at least -20ºC, more frequently even at least -10 ° C, especially at least 0 ° C being frequent. The Tg of the hydrophobic polymeric binder (a) can range from any combination of these values including the values cited.

The microparticles also comprise at least a hydrophobic crosslinking agent (b) containing groups functional reactants with the functional groups of the binder hydrophobic polymer (a). The selection of agents hydrophobic crosslinking suitable for use in dispersions thermostable of the present invention depends on the groups functional reagents associated with component (a).

Among hydrophobic crosslinking agents Suitable include those described above. If desired, you can use mixtures of hydrophobic crosslinking agents.

As mentioned before, the dispersion of the polymeric microparticles is prepared by mixing the components (a) and (b) that have been described under high conditions Shears. As used herein, the expression "conditions of high shear "aims to include not only high techniques tension, such as entrapment techniques liquid-liquid described in more detail more forward but also high speed shear with media mechanics It should be understood that, if desired, it can be used any mode of application of tension to the mixture of pre-emulsification as long as a enough tension to get the size distribution of necessary particle.

Generally, the dispersion of the next way. The hydrophobic polymer binder is mixed (a) and the hydrophobic crosslinking agent (b) and, if desired, other ingredients as neutralizing agents, surfactants external, catalysts, flow additives and the like, with water, with stirring, to form a mixture of pre-emulsion oil in water semi-stable You can add component (c) to the pre-emulsion at this point. While you can stabilize the pre-emulsion mixture using external surfactants, for the purposes of this invention is not preferable. Then, the mixture of pre-emulsion at a sufficient tension to carry out the formation of polymeric microparticles of a uniformly fine particle size; then they are removed residual organic solvents azeotropically by distillation under reduced pressure, at low temperature (i.e. less 40 ° C) to produce a stable dispersion, without solvent, substantially organic polymeric microparticles.

For the present application, the binder substantially hydrophobic polymer (a) (or monomers ethylenically unsaturated used to prepare the binder polymeric (a)) together with the hydrophobic crosslinking agent (b) They are called organic component. The organic component comprises generally also other organic species.

The dispersions of this embodiment of the present invention are typically prepared as emulsions oil in water That is, the aqueous medium provides the phase continuous in which the polymeric microparticles are suspended as an organic phase

The aqueous medium generally consists exclusively in water. However, for certain systems of polymer, it may be desirable to also include a smaller amount of an inert organic solvent that may favor the reduction of the viscosity of the polymer to be dispersed. Typically, the amount of organic solvent present in the aqueous dispersion of the present invention is less than 20 percent by weight, normally less than 5 percent by weight, being mostly frequent less than 2 percent by weight based on total weight of the dispersion. For example, if the organic phase has a Brookfield viscosity greater than 1000 centipoise at 25 ° C or a W Gardner-Holdt viscosity, some can be used solvent Among the examples of suitable solvents that they can incorporate into the organic component include xylylene, methyl isobutyl ketone and n-butyl acetate.

As mentioned above, preferably, the mixture is subjected to an appropriate tension through the use of a MICROFLUIDIZER® emulsifier that is commercially distributed by Microfluidics Corporation in Newton, Massachusetts. The MICROFLUIDIZER® high pressure trap emulsifier is described in detail in US Pat. No. 4,533,254. The device consists of a high pressure pump (up to approximately
1.4 x 10 5 kPa (20,000 psi)) and an interaction chamber in which emulsification takes place. The pump forces the mixture of reagents into the aqueous medium in the chamber where it is divided into at least two streams that pass at a very high speed through at least two slots and are crushed to form small particles. In general, the pre-emulsion mixture passes through the emulsifier at a pressure between about 3.5 x 10 4 and about 1 x 10 5 kPa (5,000 and 15,000 psi). Multiple steps may result in smaller average particle sizes and a narrower interval for particle size distribution. When the aforementioned MICROFLUIDIZER® emulsifier is used, the liquid-liquid entrapment tension is applied as described. As mentioned above, other ways of applying tension to the mixture in pre-emulsification can be used as long as sufficient tension is applied to achieve the necessary particle size distribution. For example, an alternative way of applying voltage would be the use of ultrasonic energy.

Tension is described as force per unit of surface. While the exact mechanisms according to which the MICROFLUIDIZER® emulsifier works in the mixture of pre-emulsification to form particles is not fully understood, the theory that tension is exerted is launched in more ways than one It is believed that one of the ways in which exerts tension is by shear; that is, the force is such that it move a parallel layer or plane to an adjacent parallel plane. Tension can also be exerted from all sides as a compression tension in volume. In this case, the tension could be Exercise without any shears. One more way to produce tension Intense is by cavitation. Cavitation takes place when the pressure inside the liquid is reduced enough to cause vaporization. The formation and crushing of steam bubbles takes place violently after a short period of time and produces intense tension. While it is not intended to establish no particular theory, it is believed that both the shear and the cavitation contribute to produce the tension that forms particles of the mixture in pre-emulsification.

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As explained above, the substantially hydrophobic polymer binder (a) can alternatively prepare in the presence of the crosslinking agent hydrophobic (b). If this method is used, they are typically combined the polymerizable ethylenically unsaturated monomers used to prepare the hydrophobic polymer binder (a) and the agent of hydrophobic crosslinking (b) with a surfactant and mix with an aqueous medium to form a mixture of pre-emulsion The flow control agent (c) It may or may not be present in the pre-emulsion. The pre-emulsion mixture is then subjected to high voltage conditions as described to form microparticles The polymerizable species within each particle are then polymerized under sufficient conditions as to produce polymeric microparticles that disperse stably in the aqueous medium.

Typically, an agent is present surfactant or dispersant to stabilize the dispersion. Normally the surfactant is present when mixed the organic component mentioned above in the aqueous medium before microparticle formation. Alternatively, you can introduce the surfactant into the medium immediately after the microparticles have formed. However, the surfactant may constitute an important part of the particle formation process and often necessary to achieve the necessary dispersion stability. The agent Surfactant can also be used to prevent the Emulsified particles form agglomerates.

Anionic, cationic surfactants and nonionic as those described above are suitable for use in the aqueous dispersions herein invention, the anionic surfactants being preferred. Other known materials are also useful for use here. People specialized in the technique. Generally they use both anionic and nonionic surfactants in combination and the amount of the surfactant ranges from about 1 percent and about 10 percent, preferably less than 2 percent, based on the percentage on the total solids

To carry out the polymerization of the ethylenically unsaturated monomers in the presence of the hydrophobic crosslinking, usually an initiator of free radicals. You can use both primers Water soluble as soluble oil. Among the examples of initiators Water-soluble ammonium peroxydisulfate are included, potassium peroxydisulfate and hydrogen peroxide. Between the oil-soluble initiators include hydroperoxide of t-butyl, dilauryl peroxide and 2,2'-azobis (isobutyronitrile). Usually, The reaction is carried out at a temperature between 20 ° C and 80 ° C. The polymerization can be carried out in a process continuous or discontinuous. The duration of time needed to carry The polymerization can vary between 10 minutes and 6 hours. The processes through which the forms can be formed polymeric microparticles are described in detail in the patent USA No. 5,071,904.

Once the microparticles have formed, and the polymerization process has been completed, the product resulting is a stable dispersion of polymeric microparticles in an aqueous medium that may contain some organic solvent. Typically, the organic solvent is removed by distillation at reduced pressure, at a temperature below 40 ° C. The product final is a stable dispersion, substantially free of organic solvent, each microparticle comprising both the substantially hydrophobic polymeric binder (a) as the agent substantially hydrophobic surfactant (2). "Scattered stably "means that polymeric microparticles do not they are deposited or coagulated or flocculated while at rest. Such as  It has been noted above, a very important aspect of polymeric microparticle dispersions is that the size of particle is uniformly reduced. Generally, the microparticles have an average diameter of approximately 0.01 micrometers to about 10 micrometers. Preferably, the average particle diameter after polymerization ranges from about 0.05 micrometers to about 0.5 micrometers The particle size can be measured with an analyzer of particle size, such as a Coulter N4 instrument commercially distributed by Coulter.

The film formation composition of the The present invention comprises an aqueous dispersion of polymeric microparticles, the film formation composition may also comprise one or more crosslinking agents hydrophilic that adapt to react with functional groups of the polymeric microparticles to provide a cure Additional film forming composition. Between the non-limiting examples of suitable crosslinking agents are include blocked polyisocyanates and aminoplast resins, such as described generally above, which are hydrophilically modified or otherwise adapted to be Water soluble or water dispersible. Crosslinking agent hydrophilic or the mixture of crosslinking agents used in the film formation composition depends on the functionality associated with polymeric microparticles. With more frenquency, The polymeric microparticles are hydroxyl and / or carbamate functional and hydrophilic crosslinking agent, when used, it is a modified blocked aminoplast or polyisocyanate hydrophilically.

A hydrophilically blocked polyisocyanate suitable for use as a hydrophilic crosslinking agent is a hydrophilically modified isocyanutate blocked with 3,5-dimethyl pyrazole diisocyanate 1,6-hexamethylene that is distributed commercially as BI 7986 from Baxenden Chemicals Ltd. in Lancashire, England. Examples of suitable aminoplast resins include those containing methylol or similar alkylol groups, having etherified a portion of them by reaction with an alcohol lower, preferably methanol, to provide a resin of water soluble / dispersible aminoplast, such as resin of CYMEL-385 partially methylated aminoplast, which It is commercially distributed by Cytec Industries, Inc. Agents Preferred hydrophilic crosslinking include polyisocyanates hydrophilically modified locks.

When employed, the crosslinking agent hydrophilic is typically present in the formation composition of film in an amount of at least 10 percent by weight, frequently between at least 10 and at least 20 percent by weight, being more frequent between at least 20 and at least 30 percent in weight based on the total weight of resin solids in the film formation composition. Crosslinking agent hydrophilic is also typically present in the composition of film formation in an amount between less than 70 and less than 60 percent by weight, often between less than 60 and less than 50 percent by weight, being more frequent among less than 50 and less than 40 percent by weight, based on the total weight of the resin solids of the film forming composition. He hydrophilic crosslinking agent may be present in the film forming composition in an amount comprised between any combination of these values including the cited intervals.

Film forming compositions curable aqueous of the present invention further comprise a copolymer flow control agent (c).

As used here, it is intended that the term "copolymer" include a synthesis copolymer as well as waste from initiators, catalysts and other elements that participate in the synthesis of the copolymer, but not incorporated in it covalently. Typically, said mixtures are mixed or combined. waste and other elements considered as part of the copolymer composition with the copolymer so that they tend to remain with the copolymer when transferred from a container to another or from one solvent medium or dispersion to another.

As used here, the expression "substantially free" serves to indicate that it is present A material such as accidental impurity. That is, the material is not intentionally added to the indicated composition, but may be present at lower levels or that do not carry consequences anymore which is dragged as an impurity as part of a component of the intended composition.

The terms "donor monomer" and "acceptor monomer" are used throughout the present request. With regard to the present invention, the term "donor monomer" refers to monomers that have a group ethylenically unsaturated polymerizable having a density of relatively high electrons in the double ethylenic bond, and the term "acceptor monomer" refers to monomers that have a ethylenically unsaturated polymerizable group having a relatively low electron density in the ethylenic bond double. This concept has been quantified to some extent by the Q-e scheme by Alfrey-Price (Robert Z. Greenley, Polymer Handbook, 4th edition, Brandrup, Immergut and Gulke, editors, Wiley & Sons, New York, N.Y. pp. 309-319 (1999)). All values c mentioned here are those that appear in the Polymers Manual unless it is Indicate otherwise.

In the Q-e scheme, Q reflects the reactivity of a monomer and e represents the polarity of a monomer, which indicates the electron density of a group ethylenically unsaturated polymerizable monomer. A value positive for e indicates that the monomer has a density of relatively low electrons and is an acceptor monomer, as is the case of maleic anhydride, which has an e value of 3.69. A value low or negative for e indicates that a monomer has a density of relatively high electrons and that is a donor monomer, as is the case of ethyl vinyl ether, which has an e value of -1.80.

As used herein, "acceptor monomer strong "includes monomers with an e value greater than 2.0. "soft acceptor monomer" refers to monomers that they have an e value greater than 0.5 up to the monomers that have a e value of 2.0 inclusive. In contrast, the term "monomer strong donor "includes monomers that have an e-value less than -1.5, and the term "soft donor monomer" includes monomers with an e-value of less than 0.5 to those with a e -1.5 value.

In the copolymer of component (c) at least one 30 mol%, in many cases at least 40 mol%, typically at minus 50 mol%, in some cases at least 60 mol% and in other cases at least 75% moles of polymer radicals are derived of alternating sequences of donor monomer pairs - monomer acceptor, which have alternating monomer radical units of structure:

- [DM-AM] -

in which DM represents a radical of a donor monomer and AM represents a radical of a monomer acceptor. The copolymer can be a 100% alternating copolymer of DM and AM. More particularly, at least 15 mol% of the copolymer comprises a donor monomer having the following structure (I):

4

wherein R 1 is an alkyl of C 1 to C 4 linear or branched, R 2 is one or more between methyl, linear, cyclic or branched C 1 to C 20 alkyl, alkenyl, aryl, alkaryl or aralkyl. Also, in a mode of particular embodiment, at least 15 mol% of the copolymer includes an acrylic monomer as a monomer acceptor

The copolymer incorporates a portion substantial alternating radicals of a mild donor monomer such as described by structure I and a soft acceptor monomer, which is an acrylic monomer. Table 2 shows a list not limited values and published for monomers that can be include as monomers described by structure I.

TABLE 2 Values and Alfrey-Price for monomers selected

5

In a particular embodiment, the copolymer component (c) is substantially free of maleate monomer radicals and fumarate monomer radicals, which typically have values e greater than 2.0. These types of multifunctional monomers provide too many groups functional for the copolymer. This can create problems, for example, in coatings in which the thermosetting composition may have a short storage life due to nature Openly functional copolymer.

Moreover, the copolymer component present (c) is typically substantially free of metals of transition and Lewis acids that, as already noted, have been used in the prior art to produce copolymers attenuators of soft donor monomers and acceptor monomers soft. The present invention does not use metal attachments of transition or Lewis acid to prepare the copolymer (c) and, by therefore, they should not be removed after polymerization, and the resulting copolymer compositions will not suffer from the problems inherent to those containing transition metals or Lewis acids.

Any donor monomer can be used suitable for preparing the copolymer (c) used in the film forming composition of the present invention. The suitable donor monomers that can be used include strong donor monomers and, more frequently monomers soft donors The copolymers present will include a monomer soft donor described by structure I, as isobutylene, diisobutylene, dipentene and isoprenol, and may additionally include other suitable soft donor monomers. The donor monomer of Structure I can have functional groups. For example, the group R 2 of the donor monomer of structure I may include one or more functional groups such as hydroxy, epoxy, carboxylic acid, ether, carbamate and amide.

The soft donor monomer of structure I is present in the copolymer composition at a level of at least 15% in moles, in some cases at least 25 mol%, typically at minus 30% in moles and, in some cases, at least 35% in moles. He soft donor monomer of structure I is present in the copolymer composition at a level of up to 50 mol%, in some cases up to 47.5 mol%, typically up to 45 mol% and in some cases up to 40 mol%. The level of donor monomer Soft structure I used is determined according to the properties which are to be incorporated into the copolymer composition. The radicals of the soft donor monomer of structure I may be present in the copolymer composition in any range of the quoted values including those cited.

Among other suitable donor monomers that may be used in the copolymer of component (c) are included, without being limited only to them ethylene, butene, styrene, styrene substituted, methyl styrene, vinyl ethers, vinyl esters, vinyl pyridines, divinyl benzene, vinyl naphthalene and divinyl naphthalene Vinyl esters include esters carboxylic acid vinyls, which include without be limited only to them vinyl acetate, vinyl butyrate, 3,4-dimethoxybenzoate vinyl and benzoate vinyl. The use of other donor monomers is optional, when other donor monomers are present, they are present at a level of at least 0.01 mol% of the copolymer composition, frequently at least 0.1 mol%, typically at least 1% in moles and, in some cases, at least 2 mol%. The other monomers  Donors can be present in up to 25 mol%, in some cases up to 20 mol%, typically up to 10 mol% and, in some cases up to 5% in moles. The level of the other monomers Donors used are determined according to the properties that are incorporated into the copolymer composition. The radicals of other donor monomers may be present in the composition of copolymer in any range of the cited values, including those cited.

The copolymer (c) includes acceptor monomers as part of the donor monomer units - acceptor monomer alternating along the copolymer chain. It can be used any suitable acceptor monomer. It should be understood that acceptor monomers as used in the preparation of copolymer should not be constructed as Lewis acids, whose use as catalysts it is not desirable in the present invention, such as explained before. Among suitable acceptor monomers strong acceptor monomers and acceptor monomers are included soft. A non-limiting class of suitable acceptor monomers are those described by structure (II):

100

in which W is selected from the group consisting of -CN, -X and -C (= O) -Y, selecting And of the group consisting of -NR 3 2, -O-R 5 -O-C (= O) -NR 3 2 and -OR 4, R 3 is selected from the group consisting of H, linear or branched C 1 -C 20 alkyl and linear or branched C 1 -C 20 alkylol, R 4 is selected from the group consisting of H, poly (oxide of ethylene), poly (propylene oxide), alkyl C 1 -C 20 linear or branched, alkylol, aryl, alkaryl and aralkyl, fluoroalkyl of C 1 -C 20 linear or branched, fluoroaryl and fluoroaralkyl, a polysilioxane radical, R 5 is a group of linear C 1 -C 20 alkyl bond or branched divalent, and X is a halide

A class of soft acceptor monomers that included in the copolymer composition are acceptor monomers Acrylics Among suitable acrylic acceptor monomers are include those that present the structure (III):

6

in which Y is selected from the group consisting of -NR3 2, -O-R 5 -O-C (= O) -NR 3 2 and -OR 4, R 3 is selected from the group consisting of H, linear or branched C 1 -C 20 alkyl and linear or branched C 1 -C 20 alkylol, R 4 is selected from the group consisting of H, poly (oxide of ethylene), poly (propylene oxide), alkyl C 1 -C 20 linear or branched, alkylol, aryl and aralkyl, fluoroalkyl of C 1 -C 20 linear or branched, fluoroaryl and fluoroaralkyl, a polysilioxane radical, R 5 is a group of linear C 1 -C 20 alkyl bond or branched divalent. A particularly useful type of monomers Acrylic acceptors is the one constituted by those described by the structure III in which Y includes at least one functional group selected from hydroxy, amide, oxazoline, acetoacetate, blocked isocyanate, carbamate and amine. Y groups can convert to salt groups selected from acid salt carboxylic, amine salt, quaternized ammonium, phosphonium quaternized and sulfonium ternary.

Among the examples of acceptor monomers suitable that can be used in component (c) of the The present invention includes, but not limited to, acrylate hydroxyethyl, hydroxypropyl acrylate, acrylate 4-hydroxybutyl, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, isobornyl acrylate, glycidyl acrylate, acrylate dimethylaminoethyl, acrylamide, perfluoromethyl ethyl acrylate, ethyl perfluoro acrylate, butyl ethyl perfluoro acrylate, trifluoromethyl benzyl acrylate, perfluoro alkyl ethyl, acryloxyalkyl terminated polydimethylsiloxane, acryloxyalkyl tris (trimethylsiloxy silane), oxide polyethylene terminated in acryloxyalkyl trimethylsiloxy, ethylene chlorotrifluoro, glycidyl acrylate, acrylate 2-ethylhexyl and n-butoxy methyl acrylamide

Acrylic Acceptor Monomers of Structure III are typically present in the copolymer composition in a level of at least 15 mol%, in some cases at least 25% in moles, often at least 30% in moles and, in some cases, at minus 35 mol% Acrylic Acceptor Monomers of Structure III are present in the copolymer composition at a level of up to 50 mol%, in some cases up to 47.5 mol%, frequently up to 45% in moles and in some cases up to 40% in moles The level of acrylic acceptor monomers of structure III used is determined according to the properties that are going to incorporate into the copolymer composition. The radicals of Acrylic acceptor monomers of structure III may be present in the copolymer composition in any range of the quoted values including the quoted values.

Other suitable mild acceptor monomers that can be used in component (c) of the present invention include, but not limited to, acrylonitrile, methacrylonitrile, vinyl halides, crotonic acid, sulfonates vinyl alkyl and acrolein. Vinyl halides include, without be limited only to them vinyl chloride and vinylidene fluoride. The use of other soft acceptor monomers is optional, when other soft acceptor monomers are present, they are present at a level of at least 0.01 mol% of the composition of copolymer, often at least 0.1 mol%, typically at minus 1% in moles and, in some cases, at least 2% in moles. The other acceptor monomers may be present in up to 35% in moles, in some cases up to 25% moles, typically up to 15% in moles and, in some cases, up to 10% in moles. The level of others acceptor monomers used is determined according to the properties which are to be incorporated into the copolymer composition. The radicals of other acceptor monomers may be present in the copolymer composition in any range of values cited, including cited values.

The copolymer (c) has a molecular weight of at minus 250, in many cases at least 500, typically at least 1000, and in some cases at least 2000. The copolymer can have a weight molecular of up to 1,000,000, in many cases up to 500,000, typically up to 100,000 and in some cases up to 50,000. Certain applications will require that the molecular weight of the copolymer present does not exceed 25,000, in some cases, which does not exceed 20,000 and, in certain cases, not exceed 16,000. He The molecular weight of the copolymer is selected based on the properties to be incorporated in the composition of copolymer The molecular weight of the copolymer may vary by any range of the quoted values, including the values cited.

The polydispersity index (PDI) of Copolymer is not always critical. The polydispersity index of copolymer is normally less than 4, in many cases less than 3.5, typically less than 3.0; and in some cases less than 2.5. Such as the "index of" is used here and in the claims Polydispersity "is determined from the following equation: (Average molecular weight (Pm) / average molecular weight in number (Mn)). A monodisperse polymer has a PDI of 1.0. For other part, as used here, Mn and PM are determined by gel permeation chromatography using patterns polystyrene.

In an embodiment of the composition of copolymer of the present invention, the alternating sequences of the donor monomer pairs - acceptor monomer are radicals that they have the alternating structure IV:

7

wherein R 1, R 2 and W are defined as in the previous case. An embodiment particularly preferable is one in which the radicals of monomer containing the group W are derived from one or more monomers acrylics and monomer radicals containing the groups R 1 and R 2 are derived from diisobutylene and / or isobutylene. The copolymer compositions used in the composition of film formation of the present invention may include other ethylenically unsaturated monomers polymerizable.

The copolymer composition may carry incorporated all monomer radicals in an architecture alternating A non-limiting example of a copolymer segment which has 100% diisobutylene alternating architecture (DIIB) and an acrylic monomer (Ac) is the one shown with the structure V:

(V) -Ac-DII-B-Ac-DIIB-Ac-DIIB-Ac-DIIB-Ac-DIIB-Ac-DIIB-Ac

However, in most cases, the copolymer will contain alternating segments and random segments as shown by structure VI, a copolymer of DIIB, Ac and other monomers, M:

8

Structure VI presents an embodiment wherein the copolymer can include alternating segments such as shown in random boxes and segments as shows in the underlined segments.

The random segments of the copolymer can contain donor or acceptor monomer radicals that have not been incorporated into the copolymer composition through a alternating architecture The random segments of the composition of copolymer can also include radicals of other monomers ethylenically unsaturated. As mentioned above, it claims that all references to polymer segments derivatives of alternating sequences of donor monomer pairs - acceptor monomer include monomer radical segments such as those shown in the boxes of structure VI.

The other ethylenically unsaturated monomers include any suitable uncategorized monomer traditionally, for being an acceptor monomer or a monomer donor

The other ethylenically unsaturated monomers, M radical of structure VI, are derived from at least one monomer polymerizable by ethylenically unsaturated radicals. As it used herein and in the claims, it is intended that "monomer polymerizable by ethylenically unsaturated radicals "and the Similar terms include vinyl monomers, allylic monomers, olefins and other ethylenically unsaturated monomers that can be polymerize by radicals and they are not classified as monomers donors or acceptor monomers.

The classes of vinyl monomers from which can derive M include, without being limited only to them, radicals of monomer derived from monomers of general formula VII:

9

wherein R 6, R 7, and R 9 are independently selected from the group consisting of eh H, CF 3, linear or branched alkyl of 1 to 20 atoms of carbon, aryl, linear or branched unsaturated alkenyl or alkynyl of 2 to 10 carbon atoms, linear or branched alkenyl unsaturated of 2 to 6 carbon atoms substituted with a halogen, C 3 -C 8 cycloalkyl, heterocyclyl and phenyl; R 8 is selected from the group consisting of H, alkyl of C 1 -C 6, and COOR 15, selecting R 15 of the group consisting of H, an alkali metal, a group C 1 -C 6 alkyl, glycidyl and aryl

Among the specific examples of methacrylates of alkyl having 1 to 20 carbon atoms in the group alkyl from which the radical M can be derived are included, without limited to them, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylate tert-butyl methacrylate 2-ethylhexyl, lauryl methacrylate, methacrylate of isobornyl, cyclohexyl methacrylate, methacrylate 3,3,5-trimethylcyclohexyl as well as methacrylates functional as hydroxyalkyl methacrylates, methacrylates with oxirane function, and methacrylates with carboxylic acid function.

M radicals can also be selected between monomers that have more than one methacrylate group, as per example methacrylic anhydride and diethylene methacrylate glycol.

As used here and in the claims, is understood as "monomer (s) acrylic (s) "monomers containing functionality substituted or unsubstituted allylic, that is, one or more radicals represented by the following general formula VIII,

(VIII) H 2 C = C (R 10) - CH 2 -

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in which R 10 is hydrogen, halogen, or a C 1 -C 4 alkyl group. Plus commonly R 10 is hydrogen or methyl and consequently the general formula VII represents the (meth) allyl radical without substitute, which encompasses both allyl and metalyl radicals. Between Examples of allylic monomers are included, but not limited to to them, (meth) allyl alcohol; (meth) allyl ethers, as methyl (meth) allyl ether, allyl esters of acids carboxylic, such as (meth) allyl acetate, butyrate (meth) allyl, 3,4-dimethoxy benzoate (meth) allyl and benzoate of (meth) allyl.

The copolymer composition used as component (c) in the film-forming composition of the The present invention is prepared through a method that includes steps of (a) providing a donor monomer composition that comprises one or more donor monomers of structure (I) and (b) adding an ethylenically unsaturated monomer composition that It comprises one or more acceptor monomers. In one embodiment of the present invention, the ethylenically monomer composition unsaturated includes monomers of structure III. The composition of ethylenically unsaturated monomer is added to the composition of donor monomer in the presence of a polymerization initiator of free radicals in a suitable reaction vessel. The monomer solutions and the resulting copolymer composition are preferably substantially free of type monomers maleate, fumarate monomers, Lewis acids and metals of transition.

In an embodiment of the present invention, the monomer of structure I is present in an excess molar depending on the amount of acrylic acceptor monomer. Be you can use any excess amount of monomer from structure I in the present invention in order to stimulate the formation of the desired alternating architecture. The amount in excess monomer of structure I can be at least 10 mol%, in some cases up to 25 mol%, typically up to 50 mol% and, in some cases, up to 100 mol%, depending on the quantity of acrylic acceptor monomer. When the molar excess of the monomer of structure I is too high, the process cannot be economical to commercial scale

In yet another embodiment of the present invention, the acrylic acceptor monomer is present in the copolymer in an amount of at least 15 mol%, in some cases 17.5 mol%, typically at least 20 mol% and, in some cases 25 mol% of the total combined donor monomer composition and ethylenically unsaturated monomer composition. The acrylic acceptor monomer may also be present in an amount of up to 50% by weight, in some cases up to 47.5 mol%, typically up to 45 mol% and, in some cases up to 40 mol% of the total composition. combined from donor monomer and ethylenically unsaturated monomer composition. The level of acrylic acceptor monomers used is determined according to the properties to be incorporated in the copolymer composition. Acrylic acceptor monomers may be present in the monomer composition in the range of the cited values, including the cited values.
two.

The monomer composition ethylenically unsaturated method of the present invention may include other monomers as described, as well as other designated monomers by M and described above. The use of others Soft acceptor monomers is optional in the method herein. invention. When other mild acceptor monomers are present, they may be present at a level of at least 0.01 mol% of the copolymer composition, often at least 0.1 mol%, typically at least 1 mol% and, in some cases, at least 2% in moles The other acceptor monomers may be present in up to 3 mol%, in some cases up to 25 mol%, typically up to 15% in moles and in some cases up to 10% in moles The level of other acceptor monomers used is determined according to the properties to be incorporated in the composition of copolymer. The radicals of other acceptor monomers can be present in the polymer composition in any of the ranges of the quoted values, including the values cited.

The use of other monomers, M is optional. When other monomers are present, they are present at a level of at minus 0.01 mol% of the copolymer composition, frequently at least 0.1 mol%, typically at least 1 mol% and, in some cases, at least 2 mol%. The other acceptor monomers they can be present in up to 3 mol%, in some cases up to 25 mol%, typically up to 15 mol% and in some cases up to 10% in moles. The level of other monomers used is determined according to the properties to be incorporated in the copolymer composition. The radicals of other monomers, M, they can be present in the monomer composition in any of the ranges of the cited values, including the values cited.

In an embodiment of the present invention, an excess of monomer of structure I is used and removes the unreacted structure I monomer from the composition of copolymer resulting by evaporation. The elimination of unreacted monomer is typically facilitated by application of vacuum to reaction vessel.

You can use any initiator of Free radicals suitable for preparing the copolymer (c). Between examples of suitable free radical initiators are include, but not limited to, radical initiators thermal free, photo-initiators and initiators redox Among the examples of free radical initiators Suitable thermal are included, but not limited to them, peroxide compounds, azo compounds, and compounds of persulfate.

Among the examples of compound initiators Suitable peroxide are included, not limited to just them hydrogen peroxide, methyl ethyl ketone peroxide, peroxides of benzoyl, di-t-butyl peroxide, di-t-amyl peroxide, peroxide dicumyl, diacyl peroxides, decanoyl peroxides, peroxides of lauroyl, peroxydicarbonates, peroxyesters, peroxides of dialkyl, hydroperoxides, peroxycetals and mixtures thereof.

Among the examples of suitable azo compounds are included, not limited only to them 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobiscyclohexanecarbonyltryl), 2,2'-azobisisobutyronitrile, dihydrochloride 2,2'-azobis (2-methylpropionamidine), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (valeronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 4,4'-azobis (acid 4-cyanopentanoic acid), 2,2'-azobis (N, N'-dimethylene isobutyramide),  dihydrochloride 2,2'-azobis (2-amidinopropane), dihydrochloride 2,2'-azobis (N, N'-dimethylene isobutyrammidine)  and 2- (carbamoylazo) -isobutyronitrile.

In the preparation of copolymer (c), the composition of ethylenically unsaturated monomer and the initiator of free radical polymerization are added separately or from simultaneously and mix with the monomer composition donor The ethylenically unsaturated monomer composition and the free radical polymerization initiator can be added to the donor monomer composition over a period of at at least 15 minutes, in some cases at least 20 minutes, typically at least 30 minutes and in some cases at least 1 hour. The composition of ethylenically unsaturated monomer and the initiator of free radical polymerization can also be added to the donor monomer composition for a period of up to 24 hours, in some cases up to 18 hours, typically up to 12 hours, and in some cases up to 8 hours. The time for the addition of ethylenically unsaturated monomer should be sufficient to maintain an adequate excess of donor monomer of structure I on the unreacted acrylic acceptor monomer to stimulate the formation of the alternating segments donor monomer - monomer acceptor The addition time will not be so long as to make the process economically unfeasible on a commercial scale. He Addition time may vary between any of the values of the cited range including the quoted values.

After mixing or during the addition and mixed, polymerization of the monomers takes place. The method polymerization can be started at any temperature adequate. The appropriate temperature for polymerization can be room temperature, at least 50 ° C, in many cases at least 60 ° C, typically at least 75 ° C and, in some cases at least 100 ° C. The suitable temperature can also be described as 300 ° C, in many cases up to 275ºC, typically up to 250ºC and, in some cases up to 225 ° C. The temperature is typically sufficient for stimulate good reactivity of monomers and initiators employees. However, the volatility of monomers and corresponding partial pressures create an upper limit practical at the temperature determined by the pressure index of the reaction vessel The polymerization temperature can vary within any range of the cited values, including the quoted values.

The polymerization can be started at Any suitable pressure. A suitable pressure for the method of the present invention may be the environment, at least 1 psi (0.60 atm), in many cases at least 5 psi (0.34 atm), typically at at least 15 psi (1,020 atm) and, in some cases at least 20 psi (1.36 atm). Suitable pressures for polymerization can further described as 200 psi (13.60 atm), in many cases 175 psi (11.9 atm), typically up to 150 psi (10.20 atm), and in some cases up to 125 psi (8.50 atm). Pressure is typically what high enough to keep monomers and initiators in liquid phase. The pressures used have an upper limit practical which is based on the pressure index of the vessel reaction used. The pressure during polymerization may vary. within any range of the cited values, including the quoted values.

The resulting copolymer can be used as starting material for the preparation of other polymers using functional group transformations through methods known in the art. The functional groups that can be introduce through these methods include carboxylic acid, salt carboxylate, amine, amine salt, quaternized ammonium, sulfonium salt, phosphate salt, epoxy, hydroxy, amide, oxazoline, acetoacetate, isocyanate, carbamate, thioether and sulfide.

For example, a copolymer comprising methyl acrylate will contain carboxymethoxy groups. The groups carboxymethoxy can be hydrolyzed into carboxy groups or can be transesterify with an alcohol to form the alcohol ester Correspondent tooth. Using ammonia, you can convert the methyl acrylate copolymer mentioned to the amide, or using a primary or secondary amine, it can be converted to the corresponding N-substituted amide. By way of similar, using a diamine such as ethylene diamine, you can convert the mentioned copolymer of the method herein invention to an N-aminoethylamide, or with ethanolamine, to an N-hydroxyethylamide. the funcionality N-aminoethylamide can also be converted to a oxazoline by dehydration. N-aminoethylamide it can also be reacted with a carbonate, such as propylene to produce the urethane function copolymer correspondent. These transformations can be carried out to convert all carbomethoxy groups or can be carried out in part, leaving some carbomethoxy groups intact.

Epoxy groups can be introduced into the copolymer (c) directly using glycidyl acrylate in the preparation of copolymer or indirectly by transformation of the functional group. An example of an indirect method is to oxidize residual unsaturation of the copolymer to epoxy groups using a peracid, such as peroxyacetic acid. Alternatively, a copolymer with carboxyl function can be prepared by hydrolysis, as written before, treat the copolymer with carboxy function with epichlorohydrin, then alkali, to produce the epoxy function copolymer. These transformations can be carry out exhaustively or partially. The copolymer with resulting epoxy function can then be reacted with the reagents with appropriate active hydrogen content to form alcohols, amines or sulfides.

Hydroxyl groups can be introduced directly using a monomer with hydroxyl function, such as hydroxyethyl acrylate, in the copolymer or can be introduced by transformation of the functional group. When treating the copolymer with carboxyl function that has been described with an epoxy, it is possible produce a polymer with hydroxyl function. Among the epoxies suitable include, but not limited to, ethylene oxide,  propylene oxide, butylene oxide and neodecanoate glycidyl

The monomers with hydroxyl function are particularly preferable for the preparation of the copolymer. Yes well it is not intended to establish a theory, it is believed that the hydroxyl functionality of the copolymer, in particular, Primary hydroxyl functionality, contributes to buckling control and to better leveling in the film formation composition curable of the present invention after application to the substrate.

The copolymers with hydroxyl function that have been described can be further reacted to form others copolymers For example, a copolymer containing hydroxyethyl groups with a carbamoylation agent such as carbamate methyl, to produce the carbamate function copolymer correspondent. With diketene or acetoacetate t-butyl, groups can also be converted hydroxyl to acetoacetate esters.

Copolymers can also be produced with isocyanate function. Copolymers containing two or more groups hydroxyl can be treated with a diisocyanate, such as diisocyanate Isophorone, to produce polymers with isocyanate function. The copolymers with primary amine function, which have been described, can phosphide to produce isocyanate functionality.

Ionic functionality can be incorporated into the copolymer (c) through any means known in the technique. Carboxylate groups can be introduced by hydrolysis of the ester groups of the copolymer followed by the reaction with a base. Amine salts can be introduced by preparing the copolymer of the present invention with an amine function acrylate, such as for example dimethylaminoethyl acrylate, followed by protonation  of the amino groups with an acid. You can also enter amine salts by reaction of a glycidyl-functional copolymer with ammonia or an amine with active hydrogen content followed by the protonation with acid. Groups with function can be entered quaternary ammonium or ternary sulfonium groups in the copolymer by treatment of an epoxy function copolymer of the method of present invention with a tertiary amine or sulfide, respectively, in the presence of a protic acid.

Generally, copolymer (c) is present in an amount between approximately 0.5 and approximately 10 percent by weight based on the total weight of the resin solids of the film forming composition, typically between about 1 and about 10 percent by weight and, more frequently, about 2.5 to approximately 10 percent by weight.

The curable composition of the present invention may optionally contain additives such as waxes, to improve sliding properties of the cured coating, additives degassing agents, such as benzoin, adjuvant resin to modify and optimize coating properties, antioxidants and agents UV light absorption. Among the examples of antioxidants and Useful UV ultraviolet absorption agents include the commercially distributed by Ciba Specialty Chemicals with the registered trademark IRGANOX and TINUVIN. These optional additives, when used, they are typically present in up to 20 per weight percent, based on the total weight of resin solids of the curable composition.

Without trying to limit yourself to a group of groups functional, there are several examples of functional groups co-reagents that can be used in the curable film forming composition of the present invention. The functional groups of the first component (a) can consist, without being limited only to them, epoxy or oxirane, acid carboxylic, hydroxy, amide, oxazoline, acetoacetate, isocyanate, methylol, methylol ether or carbamate. The crosslinking component (b) has at least two functional groups that are co-reactive with the functional groups of the first reagent and may consist of, but not limited to, epoxy or oxirane, carboxylic acid, hydroxy, isocyanate, isocyanate topped, amine, methylol, methylol ether and beta-hydroxy alkylamide.

The film formation composition of the present invention is preferably used as a layer transparent in a coating composition composed of several components, such as the coating system "color more transparent ", which includes at least one pigmented base coat or with color and at least one transparent top layer. In this mode embodiment, the film formation composition transparent may include an aqueous composition according to the present invention.

The film formation composition of the base layer in the system more transparent color may consist of any of the compositions useful in applications of coating, in particular applications for cars. The film forming composition of the base layer comprises a Resinous binder and a pigment that act as a dye. The Particularly useful resin binders are polymers Acrylics, polyesters, including alkyds and polyurethane. The polymers prepared using radical polymerization by Atomic transfer can also be used as binders resinous in the base layer.

The base layer compositions can go supported in solvent or in water. The base support layers aqueous in the most transparent color compositions are described in US Pat. No. 4,403,003, and resinous compositions used to prepare these base layers can be used in the practice of the present invention. They can also be used aqueous support polyurethanes such as those prepared in accordance to the US patent No. 4,147,679 as a resinous algutinant of the base layer They can also be used as the base layer aqueous support coatings such as those described in the patent USA No. 5,071,904.

The base layer contains pigments to give color. Suitable pigments include those mentioned above. In In general the pigment is incorporated into the coating composition in amounts of about 1 to 80 percent by weight in Resin solids weight function. Pigment is used metallic in amounts of approximately 0.5 to 25 percent in weight depending on the weight of the coating solids.

If desired, the coating composition base may contain other additional materials known in the technique of formulating surface coatings, including those described above. These materials they can constitute up to 40 percent by weight of the total weight of The coating composition.

Base coating compositions may apply to various substrates to which they adhere through conventional means, but more often they are applied by sprayed Spraying techniques and equipment can be used for pneumatic spraying and electrostatic spraying usual, as well as manual and automatic methods.

During the application of the composition of the base layer on the substrate, a base layer is formed on the substratum. Typically, the thickness of the base layer will be approximately 0.01 to 5 mils (0.254 to 127 myrometers), preferably 0.1 to 2 mils (2.54 to 50.8 micrometers) of thickness.

After applying the base coat on the substrate, a film is formed on the surface of the substrate removed the solvent from the base layer film by heating or with a period of air drying sufficient as to ensure that the transparent layer can be applied on the base layer without dissolving the composition of the base layer, but on the other hand, without completely healing the base layer. You can apply more than one base layer and several transparent layers to achieve an optimal appearance. Normally, between the layers, it condition the layer that has been applied previously.

The layer composition can be applied transparent top on the base coated substrate through any of the conventional coating techniques, such as application by brush, spray, immersion or flow, although they are spray applications are preferable since a superior brightness You can apply any of the techniques of sprayed, such as sprayed by compressed air, or sprayed electrostatic and through both manual and manual methods automatic

After application of the layer composition transparent on the base layer, the substrate can be heated coated to cure the coating. In the curing operation, the solvents are removed and the materials of the crosslinked film formation of the composition. Heating or curing operation is usually carried out at a temperature within the interval between at least the temperature environment (in the case of cross-linking agents without polyisocyanate) at 350ºF (ambient at 177ºC) but, if necessary, they can be used lower or higher temperatures as needed to activate the mechanisms of crosslinking.

The aqueous film forming composition of the present invention has a better buckling resistance when applied on vertically oriented substrates, as well as better resistance to bulging compared to conventional film forming compositions that do not contain the copolymer component (c).

The present invention is described more fully. particular with the following examples. Unless specified otherwise, all parts and percentages are by weight.

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Examples A and B

Examples A and B illustrate the preparation of copolymers containing isobutylene or diisobutylene according to The present invention. Reagents were combined as describe below:

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To prepare the copolymer of example A, added charge # 1 to the reaction vessel equipped with a stirrer, a thermocouple and a nitrogen inlet. The vessel, the solution was placed under a nitrogen atmosphere and It was heated to 150 ° C. Charge # 2 was added to the reaction vessel over 2.5 hours. 15 minutes after starting charge # 2, charges # 3 and # 4 were started over a period of 2 hours. During the periods of addition, the temperature was maintained from the reactor at between 140 and 160 ° C and the pressures were varied between 5 psi (0.34 atm) and 62 psi (4.21 atm). Once charge # 2 is completed, The reaction mixture was maintained 2 hours at 150 ° C. They were determined the solids keeping a sample at 110 ° C for one hour and Calculating weight loss. Molecular weight was determined by gel permeation chromatography using patterns polystyrene. The equivalent weight in COOH was determined by titration with 0.1N methane KOH and it was observed to be 2604 grams / COOH in processed solids.

To prepare the copolymer of example B. Charge # 1 was added to a reaction vessel equipped with a stirrer, a thermocouple and a nitrogen inlet. The vessel was sealed, the solution was placed under a nitrogen atmosphere and heated to 150 ° C. Charge # 2 was added to the reaction vessel for 2.5 hours. 15 minutes after starting charge # 2, charges # 3 and # 4 were started for a period of 2 hours. During the periods of addition, the reactor temperature was maintained between 140 and 160 ° C and the pressures were varied between 405 psi (27.55 atm) and 360 psi (24.49). After loading # 2 was completed, the reaction mixture was maintained 2 hours at 140 and 160 ° C. The solids were determined by maintaining a sample at 110 ° C for one hour and calculating the weight loss. Molecular weight was determined by gel permeation chromatography using polystyrene standards. The equivalent weight in COOH was determined by titration with 0.1N methane KOH and it was found to be 2611 grams / COOH in solids
processed.

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Example C

This example illustrates the preparation of a acrylic latex for use as a resinous binder in film forming compositions,

eleven

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Notes:

1 Copolymer prepared from hydroxyethyl methacrylate, acrylate 2-ethylhexyl, styrene, acrylic acid, CARDURA E (glycidyl esters of aliphatic carboxylic acid mixtures tertiary, commercially available from Shell Chemical Company) in a weight ratio of 19.90: 10.15: 30.30: 11.00: 28.65, 64 per weight percent solids in methyl isobutyl ketone.

2 Isocyanurate of 1,6-hexamethylene diisocyanate blocked with 3,5-dimethyl pyrazole, at 70% solids in methyl isobutyl ketone, distributed by Baxenden Chemicals Limited, England.

^ 3 Available by Ciba-Geigy Corporation

4 Tertiary amine light stabilizer sterically hindered distributed by Cibay Geigy Corporation

5 Distributed by BYK Chemie USA

6 Distributed as a 60% solution of DuPont solids

7 Alcohol Surfactant acetylenic distributed by Air Products and Chemicals Co.

8 aliphatic hydrocarbon, distributed by Crucible Chemical

Charges # 1 and # 2 were added to the flask of reaction in order and mixed until homogeneous. Be Heated load # 4 separately at 25 ° C at 350 rpm. The Mix charge # 1 and # 2 to charge # 4 for 1 hour. When the addition was complete, load # 3 was added as a rinse to the flask and the mixture was maintained for at least 30 minutes. He passed the mixing through a Microfluidizer® homogenizer (distributed by Microfluidics Corporation) at 11,500 psi (0.78 atm) with water cooling Load # 5 was continued as a rinse through the homogenizer and the entire mixture was prepared for total distillation Then load # 6 was added to the batch with stirring (350 rpm). A nitrogen sweep was started, followed vacuum at 450-550 mmHg. The batch was heated to 40 ° C, increasing the temperature as necessary (max 60 ° C). Be slowly increased the vacuum as necessary; > 100 mm Hg, using N2 to control the foam.

Deionized water was added as necessary to adjust solids to 46.0 ± 1.5%. He cooled the reaction product at <40 ° C, then filtered to through a 5 micrometer filter bag (with sleeve). The resulting dispersion had a resin solids content of approximately 46%, a pH of 8.7, and a particle size of approximately 1600 Angstroms.

Examples 1 to 10

Examples 1 to 10 serve to illustrate the preparation of curable film forming compositions. The Examples 1 to 6 are controls and do not contain monomer copolymers. Isobutylene type. Examples 2 to 5 illustrate the preparation of curable film forming compositions in which use increasing levels of copolymers containing diisobutylene according to the present invention. Examples 7 to 10 illustrate the preparation of formation compositions of curable film in which increasing levels of copolymers containing isobutyllen according to the present invention.

The ingredients were combined as describe below:

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^ {*} RS / TW: The first number registered is the resin solids weight of the ingredient that is added to the formulation; The second number registered is the total weight of the ingredient that is added to the formulation.

1,2 Acrylic latex: aqueous acrylic resin prepared as in example C, with a solids content of a 44.5 percent by weight and 49.9 percent by weight, respectively.

3 Dynol® 604: ethoxylated acetylenic diol distributed by Air Products and Chemicals Inc.

4 Cymel® 327: Melamine Resin formaldehyde with high imino content highly methylated in isobutanol distributed by Cytec Industries, Inc.

5 Aerosil® 200 distributed smoked silica by Degusssa Corporation

6 Borchi Gel® LW 44 distributed by Borchers

7 Viscosity measured using cup # 4 Din

In a first pre-mix, Cymel® was stirred 327 and Arosil® 200 added in a ratio of 90:10 (Cymel® 327: Aerosil® 200). Next, the mixture was combined in a mill pigment dispersion (Eiger mill) to get a Hegan value of 7+. In a second previous mixture, 0.2 parts of acid were stirred dodecylbenzenesulfonic acid while adding slowly dimethylethanolamine (50% deionized water). In a third mix prior, 0.24 parts of Borchi Gel® LW 44 were shaken at the same time that deionized water was added until the premix had a uniform consistency

The acrylic latex was placed with stirring and Dynol® 604 was added. The mixture was allowed to stir to ensure complete incorporation The following ingredients were added in order with moderate agitation: monoisobuirate of 2,2,4-trimethyl-1, 3-pentanediol, isobutyl alcohol, alcohol isostearyl and the copolymer of example A. It was again allowed to Stir the mixture to ensure complete incorporation. Be added the following ingredients separately with stirring after each addition: deionized water, premix 1 and premix 2. Premix 3 was used to adjust the viscosity.

13

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The formation compositions of examples 1-10 movie about two games per separated from base and primed coated steel substrate panels to perform property tests. Primers used on the substrate are distributed commercially by PPG Industries, Inc. and are identified as 1177225AR and GPX05379. In one of the sets of panels, the base layer used on the substrate It is commercially distributed by PPG Industries, Inc. and is Identify as EWB Silver. In a second set of panels, the layer base used on the substrate is distributed commercially by PPG Industries, Inc. and is identified as EWB Black. They were applied by spraying the film forming compositions in two layers of examples 1-10 on steel panels a a temperature of approximately 24 ° C (75 ° F). He left a time of conditioning of approximately 90 seconds between the two layers. Then, the air was allowed to air resulting coating at 24 ° C (75 ° F) for 10 minutes before Baked in two stages to cure forming compositions of movie. The first stage consisted of baking for 10 minutes at 80ºC (176ºF) and the second stage, in a 22 bake minutes at 145 ° C (293 ° F).

Appearance properties were measured and Physical panels of coated panels as described in the following tests. DOI (image sharpness) was measured using a Dorigon II® DOI meter from Hunter Lab. The brightness was measured Speculate at 20º and turbidity with a Turbidity Brightness meter BYK Gardner®.

Higher brightness and DOI indices indicate Better performance Higher turbidity values indicate a greater degree of turbidity or lack of clarity. The uniformity of transparent coatings using a Byk Wavescan Plus® instrument in which the results are recorded such as long wave and short wave numbers and voltage values. The lower longwave and shortwave numbers indicate more movies uniforms Higher voltage values also indicate more uniform movies. Hardness was determined according to ASTM D 2134.

Clarity (L) was determined using a MacBeth Color Ee® 3000 spectrophotometer, distributed in the trade by Macbeth division of Kollmorgen Instruments. They were taken the clarity measures before and after the tests of humidity and the difference (dL) was also recorded. One more dL value close to zero (positive or negative) indicates a better performance.

The stain test is based on the method of Mercedes PBO 27971 chemical resistance tests. In the tests the BYK Gardner® model 2615 gradient furnace was used. This gradient oven has a differential temperature of 1ºC per element and a constant gradient greater than 36 ° C. Behind the cured, the steel test panels are allowed to condition coated at room temperature for at least 72 hours before Of the test.

Stain test with sulfuric acid

A 1% solution of sulfuric acid is applied on drop-coated steel test panels of 25 microliters using a 4780 multipipette. These apply drops leaving a distance of one centimeter between the drops. This procedure allows a temperature range of approximately  30 ° C to 74 ° C. The test panels are exposed to the drops of sulfuric acid for thirty minutes. Then it rinse the drops with cold water and dry carefully using a soft paper towel. The temperature of this first observable change in the panel of the Test like stain resistance with sulfuric acid.

Water stain test

Deionized water is applied as drops of 250 microliters using a 4780 multipipette. These drops are applied leaving a distance of two centimeters between the drops. Is done the initial water spot with a temperature range of 30 ° C to 74 ° C If no changes are observed, then the tests are repeated at a range of 60 ° C to 104 ° C. The test panels of steel coated with water drops for thirty minutes. TO then the drops are rinsed with cold water and Dry carefully using a soft paper towel. Be records the temperature of the first observable change in the panel Test as water stain resistance.

Scratch resistance (defect) of Coated test panels using the following method: measured the initial 20º brightness of the coated panels. Be scratched the coated panels by performing a linear scratch on the surface coated with an abrasive paper Lightweight of ten double rubs using a test apparatus striped AATCC Atlas®, model CM-5 distributed in the trade by Atlas Electrical Devices Company of Chicago, Illinois. The abrasive paper used consisted of sheets of sandpaper of 9 micrometers 3M 281Q WETORDRY ™ PRODUCTION ™, which is distributed in commerce by 3M Company of St. Paul, Minnesota. TO the panels were then rinsed with water with base drying of small blows carefully. The brightness was measured at 20 ° over the striped area of each panel. The registered number is the percentage of initial brightness retained after scratch test, is say, 100% X scratched brightness / initial brightness. The scratch resistance in weather conditions (resistance to retained scratch) using a scratch test method such as described after submitting the test panels without scratch in simulated weather conditions with QUV® exposure to UVA-340 bulbs in an outdoor cabin commercially distributed by Q Panel Co. The test was carried out  as follows: a cycle was carried out at 70 ° C for 8 hours followed by 50 ° C for 4 hours (total exposure time of 100 hours). The registered number is the percentage of the initial brightness retained after the scratch test retained, ie 100 x brightness scratched retained / initial brightness.

The resistance to moisture / cross-scratch adhesion of the cured film to substrate after 240 hours in a constant humidity chamber that operated at 100% relative humidity and 37.8ºC (100ºF) as It is defined in ASTM 3359-B. A rating of 100 means a loss of complete adhesion and an assessment of 0 means no loss of adhesion.

The test results for Cured compositions are those shown in the following boards.

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TABLE 1

14

TABLE 2

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TABLE 3

16

TABLE 4

17

The data in these tables indicate that curable film forming compositions prepared with according to the present invention they show properties enhanced as tested by the exploration measures of minor shortwave, without a significant loss of others Essential properties, such as brightness, DOI, resistance to defects and resistance to acid etching.

Claims (38)

1. A film formation composition curable aqueous comprising: a) a polymeric binder containing two or more reactive functional groups; b) a curing agent that has at least two functional groups that are reactive with the functional groups reagents of (a); Y c) a copolymer flow control agent that it comprises at least 30 mol% of radicals having the next alternating structure - [DM-AM] - in which DM represents a radical of a donor monomer and AM represents a radical of a monomer AcceptorM; having at least 15 mol% of the copolymer that comprises donor monomer the following structure (I): 18 wherein R 1 is an alkyl of C 1 - to C 4 linear or branched, R 2 is selected from group consisting of methyl, linear C 1 to C 20 alkyl, cyclic or branched, alkenyl, aryl, alkaryl or aralkyl 2. The film formation composition of the claim 1 wherein at least 15 mol% of the copolymer It comprises an acrylic monomer as an acceptor monomer. 3. The composition of film formation, in which the copolymer contains at least one salt group or a group of salt formation 4. The film formation composition of the claim 1, wherein the copolymer contains functionality hydroxyl 5. The film formation composition of the claim 1, wherein the copolymer is substantially free of maleate monomer segments and monomer segments of fumarate 6. The film formation composition of the claim 1, the copolymer composition being substantially free of Lewis acids and metals from transition. 7. The film formation composition of the claim 1, wherein the donor monomer is one selected from the group consisting of isobutylene, diisobutylene, dipentene, isoprenol and mixtures thereof, optionally, in combination with styrene, substituted styrenes, methyl styrene, vinyl ethers and vinyl pyridine 8. The film-forming composition of the claim 1, wherein the R2 group of the donor monomer of structure I includes one or more selected functional groups from the group consisting of hydroxy, epoxy, carboxylic acid, ether, carbamate and amide. 9. The film-forming composition of the claim 1, wherein the acceptor monomer comprises one or more described by structure (I): 101 in which W is selected from the group consisting of -CN, -X and -C (= O) -Y, selecting And of the group consisting of -NR 3 2, -O-R 5 -O-C (= O) -NR 3 2 and -OR 4, R 3 is selected from the group consisting of H, linear or branched C 1 -C 20 alkyl and linear or branched C 1 -C 20 alkylol, R 4 is selected from the group consisting of H, poly (oxide of ethylene), poly (propylene oxide), poly (caprolactone), linear or branched C 1 -C 20 alkyl, alkylol, aryl, alkaryl and aralkyl, fluoroalkyl of C 1 -C 20 linear or branched, fluoroaryl and fluoroaralkyl, a polysilioxane radical, R 5 is a group of linear C 1 -C 20 alkylene bond or branched divalent, and X is a halide 10. The film formation composition of claim 2, wherein the acrylic monomer is one or more described by structure (III): 19

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in which Y is selected from the group consisting of -NR3 2, -O-R 5 -O-C (= O) -NR 3 2 and -OR 4, R 3 is selected from the group consisting of H, linear or branched C 1 -C 20 alkyl and linear or branched C 1 -C 20 alkylol, R 4 is selected from the group consisting of H, poly (oxide of ethylene), poly (propylene oxide), alkyl C 1 -C 20 linear or branched, alkylol, aryl, alkaryl and aralkyl, fluoroalkyl of C 1 -C 20 linear or branched, fluoroaryl and fluoroaralkyl, a polysilioxane radical, R 5 is a group of linear C 1 -C 20 alkylene bond or branched divalent 11. The film formation composition of claim 10, wherein Y includes at least one group functional selected from the group consisting of hydroxy, amide, oxazoline, acetoacetate, blocked isocyanate, carbamate and amine. 12. The film formation composition of claim 3, wherein the salt group is selected from the class consisting of carboxylic acid salt, amine salt, ammonium quaternized, quaternized phosphonium and ternary sulfonium. 13. The film formation composition of claim 1, wherein the copolymer has a weight molecular range between 250 and 100,000. 14. The film formation composition of claim 1, wherein the copolymer has an index of polydispersity of less than 4. 15. The film formation composition of claim 1, wherein the structural units Alternates comprise at least 50 mol% of the copolymer. 16. The film formation composition of claim 1, wherein the acceptor monomer is one or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, acrylate 4-hydroxybutyl, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, isobornyl acrylate, dimethylaminoethyl acrylate, acrylamide, ethylene chlorotrifluoro, glycidyl acrylate, acrylate 2-ethylhexyl and n-butoxy methyl acrylamide 17. The film formation composition of claim 1, wherein the copolymer comprises one or more radicals derived from other ethylenically unsaturated monomers of general formula VII: twenty wherein R 6, R 7, and R 9 are independently selected from the group consisting of H, CF 3, linear or branched alkyl of 1 to 20 atoms of carbon, aryl, linear or branched unsaturated alkenyl or alkynyl of 2 to 10 carbon atoms, linear or branched alkenyl unsaturated of 2 to 6 carbon atoms substituted with a halogen, C 3 -C 8 cycloalkyl, heterocyclyl and phenyl; R 8 is selected from the group consisting of H, alkyl of C 1 -C 6, and COOR 15, selecting R 15 of the group consisting of H, an alkali metal, a group C 1 -C 6 alkyl, glycidyl and aryl 18. The film formation composition of claim 17, wherein the ethylenically monomers unsaturated are one or more selected from the group consisting of methacrylic monomers and allylic monomers. 19. The film formation composition of claim 1, wherein the components (a) and (b) are substantially hydrophobic and are prepared as an aqueous dispersion comprising polymeric microparticles, said preparations being prepared microparticles by mixing components (a) and (b) in high shear conditions, and being able the composition of film formation of forming a generally continuous film to room temperature. 20. The film formation composition of claim 19, wherein the functional groups of the polymeric binder (a) are selected from the group consisting of hydroxyl, carbamate, blocked isocyanate, primary amine, amine secondary, amide, urea, urethane, vinyl and mixtures thereof. 21. The film formation composition of claim 19, wherein the polymeric binder (a) It contains carbamate functional groups. 22. The film formation composition of claim 21, wherein the polymeric binder (a) It comprises the reaction product of the following reagents: 1) at least one ethylenically monomer polymerizable unsaturated containing group with acid function that  then neutralizes at least partially with a base to form carboxylic acid salt groups; 2) at least one ethylenically monomer unsaturated containing polymerizable functional group free of groups with acid function. 23. The film formation composition of claim 22, wherein the reagent (1) comprises a ethylenically unsaturated monomer containing acid group carboxylic. 24. The film formation composition of claim 23, wherein reagent (1) is selected from group consisting of acrylic acid, methacrylic acid and mixtures of they. 25. The film formation composition of claim 22, wherein the reagent (1) is present in the polymeric binder (a) in an amount sufficient to provide an acid number of up to 50 mg KOH / g. 26. The film formation composition of claim 22, wherein the reagent (2) comprises at least a monomer with hydroxyalkyl function selected from the group that consists of (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) acrylate 4-hydroxybutyl and mixtures thereof. 27. The film formation composition of claim 22, wherein the reagent (2) comprises a monomer with beta-hydroxy ester function ethylenically unsaturated. 28. The film formation composition of claim 27, wherein the monomer with function ethylenically unsaturated beta-hydroxy ester comprises the reagent reaction product selected from the group consisting of the following: 1) an ethylenically epoxy monomer unsaturated and a saturated carboxylic acid having at least 5 carbon atoms; Y 2) a monomer with ethylenically acid function unsaturated and an epoxy compound containing at least 5 atoms of carbon that is not polymerizable with the acid-function mono'mer ethylenically unsaturated. 29. The film formation composition of claim 22, wherein the reagents of which it is formed the polymeric binder (a) further comprise a reagent (3) at least one polymerizable ethylenically unsaturated monomer different from (1) and (2) 30. The film formation composition of claim 29, wherein the reagent (3) is selected from group consisting of vinyl aromatic monomers, alkyl esters of (meth) acrylic acid and mixtures thereof. 31. The film formation composition of claim 22, wherein the polymeric binder (a) is present in the dispersion in an amount between 55 and 99% by weight based on the total weight of the resin solids of the dispersion. 32. The film formation composition of claim 19, wherein the crosslinking agent (b) is select from the group consisting of blocked isocyanates, resins of aminoplast and mixtures of them. 33. The film formation composition of claim 32, wherein the crosslinking agent (b) is a 1,6-hexamethylene diisocyanate isocyanurate reversibly blocked with 3,5-dimethyl pyrazole 34. The film formation composition of claim 19, wherein the crosslinking agent (b) is present in the dispersion in an amount between 1 and 45 weight percent based on total solids weight of resin present in the dispersion. 35. The film formation composition of claim 19, further comprising at least one agent of hydrophilic crosslinking. 36. The film formation composition of claim 35, wherein the hydrophilic crosslinking agent is selected from the group consisting of blocked polyisocyanates hydrophilically modified, aminoplast resins, compounds of tricarbamoyl triazine and mixtures thereof. 37. The film formation composition of claim 35, wherein the hydrophilic crosslinking agent is present in the film forming composition in a amount of up to 70 percent by weight based on total weight of the resin solids present in the composition. 38. A coating composed of several components comprising a base deposited from a film formation composition and a top layer transparent applied on the base layer depositing the layer transparent top from a formation composition of film that is substantially free of organic solvent, said layer film forming composition comprising superior a curable aqueous film forming composition according to any of claims 1 to 37.